Preparation of novel silalkylene compositions



United States Patent 3,187,032 PREPARATEQN OF NQVEL SILALKYLENE CGWOSHIUNS Donald R. Weyenherg, Midland, Mich, assignor to The Dow Corning Corporation, Midland, Mich, a corporation of Michigan No Drawing. Filed July 3, 1961, Ser. No. 121,316 15 Claims. (Ci. Zea-44am This invention relates to a method of preparing silalkylene copolymers from halogenosilanes and/or halogenosiloxanes with certain substituted ethenes. This invention further relates to some of the novel copolymers which have been prepared by this method.

This application is a continuation-in-part of my copending application Serial Number 55,166, now abandoned, filed September 12, 1960, as a continuation-inpart of my then copending application Serial Number 29,185, filed May 16, 1960, and now abandoned.

More specifically, this invention relates to the method which comprises reacting in a solvent solution in contact with an alkali metal an or anosilicon compound (1) selected from the group consisting of halogenosilanes of the formula R SiX. and halogenosiloxanes of the formula R X Si[OSiR X in which each R is a monovalent hydrocarbon radical free of aliphatic unsatur-ation or a functional substituent which can be either the hydrogen atom or an OR radical in which R is a monovalent hydrocarbon radical free of aliphatic unsaturation, each X is a halogen atom, such a chlorine, bromine, iodine or iiuorin each m is a positive integer from 2 to 3 inclusive and each n is a positive integer, and (2) a compound (a) of the formula R" C CHR in which from one to two R" substituents are phenyl radicals and any remaining R substituent is a hydrogen atom or a methyl radical, there being no more than a total of two phenyl and methyl radicals, or (2) a compound (b) of the formula RCH=CH in which R' is a vinyl radical or an alpha-methylvinyl radical.

The solvent employed in this method can be any true organic solvent, i.e. a liquid unreactive to the system out capable of dissolving the organic organosilicon components. The commonest solvents are the Well-known hydrocarbon solvents such as, for example, xylene, benzene, toluene, hexane and cyclopentane.

Another class of solvents which are operative in this method are others, both monoethers and polyethers, each free of aliphatic unsaturation. For example, the ethers can be dimethyl ether, ethylmethyl ether, diethyl ether, di-n-propyl ether, l-methoxypentane, tetrahydrofuran, tetrahydropyran, 2-butoxymethyltetrahydrofuran, the dimethyl ether of ethylene glycol, the diethyl ether of ethylene glycol and bisbeta-ethoxyethyl ether. Preferably, the ether is a cyclic ether or a linear ether in which there is at least one ethereal oxygen atom to which is attached at least one group of no more than two carbon atoms, e.g. the methyl and ethyl groups. Also preferred are the linear polyethers having a carbon to oxygen ratio of less than 5:1, more preferably less than 3:1.

The alkali metals employed herein are well known. Since the reaction involved apparently takes place at the alkali metal surface, the alkali metal is usually added as a free metal or a suspension o-f free metal in some solvent soluble solid or liquid.

In the organosilicon compound (1) R can be, for example, any alkyl radical such as methyl, ethyl, isopropyl, tert-butyl, Z-ethylhexyl, dodecyl, octadecyl and myricyl radicals; any cycloalkyl radical such as the cyclopentyl and cyclohexyl radicals, any aryl radical such as the phenyl radical; any aralkyl radical such as the henzyl, phenylethyl and xylyl radicals and any alkaryl radical such as the tolyl and dimethylphenyl radicals; the hydro- 3,187,332 Patented June 1, 1965 gen atom or an OR' radical in which R' can be any monovalent hydrocarbon radical free of aliphatic unsaturation such as those shown above for R.

The organosilicon compound (1) can have such con-- figurations as, for example: R SiX R SiX,

XSiR (OSiR X and R Si(OSiR X where R, X and n are as defined above. These materials can all be prepared by well known methods.

Compound (2) in the method of this invention can be (a) a phenyl-substituted ethene of the formula RIIZICZCHRII in which at least from one to two R" substituents arephenyl radicals and any remaining R" substituent is a hydrogen atom or a methyl radical, there being no more than a total of two phenyl and methyl radicals. This definition includes compounds such as, for example: PhCH CH PhMeC Cl-l PhC=CH PhCH=CHpH and PhCH=CHMe, in which Ph and Me represent the phenyl and methyl radicals respectively. Compound (2) can also be (12) a low molecular weight conjugated olefin of the formula R"CH=CH in which R is a vinyl radical or an alpha-methylvinyl radical. This definition includes butadiene and isoprene. These materials are all well known.

The method of this invention can be a one-step process or a multiple step process. The multiple step process is preferred for preparing block copolymers since such a process gives the greatest product control. More explicitly, block copolymers can best be prepared by polymerizing compound (2) to the desired polymer size in an ether solvent in contact with an alkali metal, adding a separately prepared chlorosilane or chlorosiloxane (l) of the desired molecular weight and configuration, adding compound (2) and allowing it to add on to the copolymer and to polymerize to the desired block, addingmore separately prepared chlorosilane or chlorosiloxane (1) and so forth until the desired block copolymers are built up. These methods are most easily employed at room temperature and atmospheric pressure, but heating, cooling, pressure and vacuum can be employed to vary the reaction if desired.

The method of this invention is useful for the preparation of copolymeric compounds composed of organ@ silicon units (1) which can have the formulae SiR or SiR [OSiR in which R, m and n are as defined above and units (2) which can be phenyl-substituted ethylene units such as, for example, -CHIh-CH -CHP-h--CHPhand CHl h-CHMeunits or units such as The copolymeric compounds containing phenyl-substituted ethylene units are more fully described in my application Serial Number 121,309, filed July 3, 1961,0313- titled Phenyl-Substituted Silalkylene Compounds, filed concurrently herewith. The fluid compounds are useful as hydraulic fluids. The solid compounds are useful as both film-forming and fiber-forming resins depending on the functionality of the starting materials.

The copolymeric compounds containing the -CH CH=CH-CH' and/or -CIl CMe=CHCH units can have organosil-icon units (1) with, for example, any of the following configurations: SiR *SiR SiR (OSiR and SiR (CSiR Where R and H are as defined above. Since R can be reaction mixture.

and the like. When any of the organosilicon units (1) A contain hydrolyzable groups, these groups can be hydroerally useful as both film-forming and fiber-forming resins depending on the functionality of the starting materials. Of primary importance are the compounds which have functional groups, i.e., Hor OR' radicals, attached to the silicon atoms. These compounds are valuable as intermediates in the preparation of chemically integrated copolymers of organosilicon compounds, primarily siloxanes, and or anic compounds such as the various rubber polymers. The siloxanes can be cocondensed with the hydrolyzed compounds of this invention while the organic compounds containing aliphatic unsaturation can be reacted with the unsaturated carbon to carbon 7 linkage. V

The following examples are merely illustrative and are not intended to limit this invention which is properly delineated in the claims, a

7 Example 1 .23 grams (1 gram-atom). of sodium metal and 108 grams (1 mol) of trimethylchlorosilane were mixed with 150 ml. (approximately 133 grams) of tetrahydrofuran. To this stirred mixture 52 grams (0.5 rnol) of styrene were added. Tl1rce products were obtained fIO'lIllhiS One was I i (CH SiCH(C H )CH Si(CI-I a liquid having the following physical properties: 7 boiling point 93 to 97 C. at 4 to 5 mm. Hg pressure; 11

1.4890 to 1.4895. The other two products were'solid isomers having the general formula:

(CH SiCH (C l-I CH CH CH (C l-I Si (CH 3 (One of the isomers had a melting point 106.5 to 108 C.,

while the other had a melting point of 50.5 to 52 C.

When the following sil-anes are substituted mol per mol 1 for the -trirnethylch1orosi1ane above, the following prod ucts resultz Y of trimethylchlorosilane were added dropwise with vigorous stirring. The solution remained a characteristic red colofthro-ughout this addition. The reaction mixture was filtered and stripped to 150 C. at 0.3 mm. Hg yielding a polymeric product consisting of a poly-oz-rnethylstyrene or" 7 to 8 units endblocked with trime'thylsilyl units as verified by silicon analysis: This solid had a melting point of approximately 80 C. was soluble in toluene and was insoluble in methanol;

When the following chlorosilanes are substituted for the trimethylchlorosilane in this preparation, the following products res'ulti Ohlorosilane roduct is produced.

A polymeric product consisting of a poly-amcthylstyrene of 7 to 8 units cndblocked with phenyldimethylsilyl units.

A polymeric product consisting of a poly-amethylstyrene of 7 to 8 units endblocked with methyldimethoxysilyl units.

(CtH5)(CH3)2 lC1 onnsicuoorrnahuh Example 3 i To a. stirred mixture of 23 grams (1 gram-atom) of" sodium metal and 250 ml. (approximately 222 grams) of tetrahydrofuran were added 59 grams (0.5 mol) of m-rnethylstyrene. To this mixture was added 108 grams (1.0 mol) of trimethylchlorosilane at a rate suflicient to maintain a colorless solution. After further stirring for two days the mixture was distilled to-yield a liquid having the following physical properties: boiling 7 point 107 to 109 C. at 4 mm. Hg; n 1.5018.

When C H CH CHCH is substituted mol per mol for the a-methylstyrenc above, p r

Example 4 To a mixture of 129 grams (111101) of dimethyldichlorosilane, 46 grams (2 gram-atoms) of sodium metal and 250 ml. ottetrahydrofuran were added 208 grams '(2 mols) of styrene over a 30 minute period with exte'rnal cooling. The mixture was filtered. The solvent was stripped frointhe liquid portion ofthe 'rnixture leaving 7 a residue which had. a silicon analysis corresponding to a polymer having the formula:

where z is a positive integer. SiO Si or SiSi linkages. a

When ClSi(CH [OSi(CH Cl is substituted mol 7 There was no evidence of per mol for the.dimethyldichlorosilane above, the resulting residue is primarily a copolymer having the approximate formula; V

' Example 5 26 grams oi/25.11161 of styrene were added: over a 30 minute period to a stirredr'nixture of 15 grams (0.65]

gram-atom) of sodium; 54.3 grams (0.5 niol) of tria Example 2" I a 118 grams- (1 mol) of a-methylstyrene were added 7 over a 30 minuteperiod to a inixtureof 11.5'g'rams (0.5

gram-atom) of sodium and 400 m1. (approximately 355 g V 7 grams) of tetrahydrofuran. About Z'I'grarns (0.25 mommixture of solid isomers obtained in Example u methylchlorosilane, 200 diet'hylether and approxi-" mately. 20 grams of rock salt. -After 24fhours the. .resulting.precipitatewas filtered Offy Distillation of the filtrate yield ed ton sicmc npcn sncn n and the Example 6 54 grams (0.5 mol) of trimethylchlorosilanc and 26 grams (0.25) of styrene were added simultaneously with stirring at 65 to 70 C. to a dispersion of 12.5 grams of sodium (as a 50 percent by weight emulsion in paraffin wax) in 110 ml. of benzene. The products isolated were the same as those in Example 1.

Example 7 When 11.8 grams (0.1 mol) of a-methylstyrene and 0.46 gram (0.02 gram-atom) of sodium metal are stirred together in 25 ml. of tetrahydrofuran until a red color appears and 1500 grams (0.01 mol) of ClSi (CH 2 [OSi (CH3 2] zozeCl (having a viscosity at 25 C. of approximately one million cs.) dispersed in 3000 ml. of tetrahydrofuran are added with vigorous stirring at a constant rate sufiiciently slow to maintain the red color as long as possible, the residue remaining after filtering the mixture and stripping the solvent from the liquid portion is primarily a copolyrner having the approximate formula:

l s 5) a) a-l where z is a positive integer.

Example 8 Q? to a mixture of 6.44 grams (0.28 gram-atom) of finely divided sodium in 88.8 grams of tetrahydrofuran at a rate sufiicient to maintain a system temperature of 30 to 31 C. 30.4 grams (0.28 mol) of trimethylchlorosilane dissolved in 26.6 grams of tetrahydrofuran were added slowly with stirring and external cooling to the reaction mixture which was then stirred for several days. An additional 21.8 grams (0.20 mol) of trimethylchlorosilane were added to the reaction mixture which was then diluted with 264 grams of n-hexane, and filtered to recover 0.7 gram of sodium. The filtrate was distilled producing two products. One product had the following characteristics: boiling point 143 to 147 C. at 4.6 to 4.8 mm. Hg. with 11 of 1.5469. Elemental analysis, infrared spectrum and gas-liquid phase chromatography, confirmed the product as 3 s e sl 2 (CGHS) The other product was 196 grams of styrene were added to a mixture of 506 grams of dimethylmethoxychlorosilane, 46 grams of sodium and 750 ml. of tetrahydrofuran with stirring and external cooling. An additional 46 grams of sodium were added, and the mixture was stirred at room temperature for two days. The mixture was then filtered and the filtrate distilled to produce:

(1) CH OSi(CH CH(C H )CH Si(CH OCH B.P.

125 to 126 C. at 6-7 mm. Hg; n 1.4958

11 cn osi or-r cmc upcn cn cmc n si (CH OCH B.P. 144 to 148 C. at 0.3 mm. Hg.

When the following silanes are substituted mol per mol for the dimethylrnethoxychlorosilane above, the following products result:

silane (CHmSiCHOCeHu) (CH3)3S1OS1(OCH3) tonnosnonmol Product CHII OSKCIIQ 21311 (05135) CI-IgSi CH3) 20 0411 CsHsO Si (CH3) 2CH(CGH5) CH2$l(CH3)zO GGI'IS CsHnO Si (CH3) gCH (C5115) C-I'IzSi (CH3) 2O 00H (CH3)3 iOSl(OCH3) (CH Osi (CH3)2CH C6H5) CHzSl (CHQ O Si (0 CH3) (CH3) 0 Sl(C H3) 3 in 35.5 grams of tetrahydrofuran were added with stirring to a mixture of 6.44 grams (0.28 gram-atom) of finely divided sodium in 88.8 grams of tetrahydrofuran at a rate sufficient to maintain a system temperature of C. 30.4 grams (0.28 mol) of trimethylchloros-ilane dissolved in 44.4 grams of tetrahydrofuran were added slowly with stirring to the reaction mixture which'was then stirred for 2 days. 2.97 grams (0.13 gram-atom) of sodium metal was recovered by filtration, and the filtrate was distilled producing a liquid product boiling at 220 to 230 C. at 0.2 to 0.3 mm. Hg. This product was recrystallized three times from ethanol producing a white crystalline solid having a melting point of 170 to 172 C. Elemental analysis and the infrared spectrum confirmed the product as 2 s s s 2 2 2- e s z- 3 3 Example 10 25 grams (0.14 mol) of trans-stilbene dissolved in 177.6 grams of tetrahydrofuran were added with stirring Example 12 199 grams dimethylchlorosilane and 104 grams of styrene were added to a mixture of 46 grams of sodium and 50 grams of rock salt in 300 ml. of tetrahydrofuran with stirring and external cooling. The mixture was stirred at least 16 hours at room temperature and was filtered. The filtrate was distilled producing:

to C. at 4-5 mm. Hg; n 1.5000

(11) A mixture of steroisomers of HSi(CH CH(C H CH CH CH(C H )SiH(CH B.P. 164 to 166 C at 45 mm. Hgyn 15348-15402.

Example 13 60 grams 1.1 mols) of butadiene were added with stirring over a .period of 2 /2 hours to a solution of 216 grams (2. mols) of trimethylchlorosilane in 266.4 grams of tetrahydrofuran containing 46 grams (2 gram-atoms) of sodium. The reaction mixture was stirred over a period of 4 to '5 days maintaining the temperature below 45 by external cooling. The reaction mixture was filtered permitting recovery of 22 grams of sodium. The filtrate was redistilled three times to give two pure products:

r) (CH SiCH CH=CHCH Si(CI-I boiling point C. at 50 mm. Hg; r1 1.4407.

aisaosa C. at 45 mm. Hg; 11 1.4585.

These structures were verified by elemental analysis,

infrared spectra and gas liquid phase chromatography.

Xylated compound condensed and cocondensed with other silanols and siloxanols to produce polymeric and copolymeric structures containing siloxane linkages.

When butadiene is substituted mol per mol for the isoboiling point 123 0.; 2 1.4453; 1.4462. The prod- 5- prene in the above preparation, the products are Example 14 V A solution of 68.1 grams (1 mol) of isoprene in 44.4 grams of tetrahydrofuran was added with stirring over (I) (CH3)2S1OH2CH=CH Bland a period of 30 minutes to a solution of 216 grams (2 (H) (OHM(OH3O)SiQHZCE=CHCH?Si(OCH3)(CH3)?- Silane Products (001111) (CHmSiBr (OaHn) (CH3)zSlCH2C [=C(CHS)CH2 K HS)2( G H) v e e +[(C6Hll) (cfimsiomcwm)=OHcH -h (CuH5CHz) (OHa)2S1C1 (CaH5CHz) (CH3)2S1OH2C(CH3)=OHCH2S (CH3)2(CH2CG 5) (061150112) (OHmsiGHzCwm)=HGHn-1z (C12H25) (CH )zS1Cl CrzHzs) (CHa)2slCHzO(OHs)=CHCH2 (C 3)2( I2 25) e V i2 25) a)zSiCHzC( a)= 2-]2 (G H )3S1Ol (CzHs)aSiCH2 C(CHs)=CHCH2 2 5)3 e e +[(C H5)aSiCHzC(OH3)=CHCHz-]g (CHa)aS1OS1(CHa)2C1 (CH3)3SlOSl(CH3)2CHzC(CH3)=CHCHzSl(CH3)2OSi(CH3)3 q [(CH SiOSi(CHs)zGHiO(CHa)=CHOHz-l2 (CeHs) (CHa)zSiCl (C0115) (OH3); SiCHzO(OHs)=CHCH2Si(CHa)z(CsHa) +[(CGH5) (oumsiomctoni)=0HCHz-1 mols) oftrimethylchlorosilane in 266.4 grams of tetra- Example 17 l ams ggilgg When the following silanes are substituted mol per mol ump so g fi 1 1 for the trimethylchlorosilane in the preparation of EX- grams 0 Ioc p 6 36 e i o e ample 14, the following products result:' 1 perature was malntalnedbetween 25 and C. by

external cooling. After over 20 hours of stirring, the E 18 7 reaction mixture was filtered. The filtrate was distilled 30 When 68 g m of lsoprene are added over a 30 mi e and Iedistilled to ive t o products, 7 7 period with external cooling to a mixture of 129 grams T CH SiCH CH CH CH Si CH RR 1040' of dimethyldlchlorosllane, 14 gramsof llthlum metal and i g g g at 0 g Z3 2a2 i45 250 ml. of tetrahydrofuran, the m xture is filtered and [(CH3)3SiCH2C(CH3) ;CHCH2 BR 0 to the solvent is stripped from the filtered liquid, the residue 5 at 40 Hg; 7113252 1.4656 V is a polymer of the general formula Elemental analysis, infrared spectra and gas liquid 3) CHC 2 ]X[ SKCHa)? 1y phase chromatography verified these structures. i Y liI 15 approximately equal to y alpldihfire a e no I in ages. 4 e

7 Example 1 40 When ClSi(CH [OSi(CH Cl is substituted mol. A'mixture of 68.1 grams (1 mol) of isoprene and 129 per mol for the dimethyldichlorosilane in the above prepgrams (1 mol) of dimethyldichlorosilane was added aration, the resulting residue is a copolymer of the general slowly with stirring'to a mixture of 46 grams of lump formula V f p e e 7 sodium inBOO ml. of tetrahydrofuran. The temperature was maintained between 25 and 35 C. with external CH2C(CH.3) CHCH2 1x 4o 7 B)2[ 3)2]3 cooling. The mixture was then stirred at room tempera e e ture for at least 16 hours. Unreacted sodium was filtered W 15 equal approxlmatelyto y and there l no out, and the filtrate was distilled producing slfsl m V V e Example 19 7 e When the following silanes are substituted mol per (CH3)2SiCH O(OH )=CH H, 00

mol for the dimethylmethoxychlorosilane in the preparation of Example 16, the following products result:

' Silan e Product (ormlsiouooim) not was verified by elemental analysis and the nuclear magnetic resonance spectrum.

Example 16.

68 grams of isoprene were added with stirring to a mixture of 248 grams of dimethylmethoxychlorosilane, 46 grams of lump sodium, 50' grams of rock salt and 300 ml. of tetrahydrofuran. This mixture was stirred at 7 room temperature for: at least 64 hours. 'Unreacted sodium was filtered producingi e out, and the filtrate was distilled 120" GLat smm. Hg; u 1.4441.

7 Compound'II can he'hydrolyz'ed andthe resulting hydro- Exam le 2 i 7 When dimethylchlorosilane is substituted mol per mol for the dimethylmethoxychlorosilane in the preparation of Example'16,

compound (1) selected from' the group'consisting 1 of haloge-nosilanes of the formula R S-iX and halogenosiloxanes of the -formula R X3 S l[OSlR ]hX in which each'R is selected from thegroup, consisting ofmonovalenthydrocarb-on radicals free of aliphatic unsaturation and functional -sub'stitu:ent 's selectedfrom the group 9 consisting of the hydrogen atom and OR' radicals in which R is a monovalent hydrecaubon radical free of aliphatic unsaturation, each X is a halogen atom, each m is a positive integer from 2 to 3 inclusive and each n is a positive integer, and a compound (2) selected from the group consisting of (a) compounds of the formula R C:CHR" in which at least one R" substituent is the phenyl radical and any remaining R" substituent is selected from the group consisting of the hydrogen atom and the methyl radical, there being no more than a total of two phe-nyl and methyl radicals, and (b) compounds of the formula RCH:CH in which each R is a substituent selected from the group consisting of the vinyl radical and the alpha-methylvinyl radical, whereby the silicon atoms of (1) are attached to aliphatic carbon atoms of (2) with the elimination of X atoms from (1% 2. A copolymeric compound firee or Si-Si bonding consisting essentially of organosilicon units (1) selected from the group consisting of units of the formulae SiR and S-iR [OSiR in which at least one R per unit is a functional substituent selected from the group consisting of the hydrogen atom and -OR radicals in which R is a monovalent hydrocarbon radical free of aliphatic unsaturation, any remaining R radicals being monovalent hydrocarbon radicals free of aliphatic unsaturation, each m is a positive integer from 2 to 3 inclusive and each n is a positive integer, and units (2) of the formula selected from the group consisting of CH CH:CHCH and CH C(CH ):CHCH

3. A copolymeric compound free of Si-Si bonding consisting essentially of organosilicon units 1) of the formula SiR' in which each R is a monovalent hydrocarbon radical flee of aliphatic unsaturation and m is a positive integer from 2 to 3 inclusive and units (2) of the formula CH --C(CH :CHCH

4. A copolymeric compound free of Si-Si bonding consisting of organosilicon units (1) of the formula --SiR in which each R is a monovalent hydrocarbon radical free of aliphatic unsaturation and units (2) of the formula CH -C(CH :CHCH

5. A copolymeric compound free of Si-Si bonding consisting of -Si(CH units and 6. A copolymeric compound free of Si-Si bonding consisting essentially of organosilicon units (1) of the forrnula SiR' in which each R is a monovalent hydrocarbon radical tree of aliphatic unsaturation and units (2) of the formula CH -C(CH ):CHCH

7. A copolymer-ic compound free of Si-Si bonding con sisting of -Si(CH units and iii sisting of organosilicon units (1) of the formula -SiR' in which each R is a monova-lent hydrocarbon radical free of aliphatic unsaturation and units (2) of the formula CH CH:CHCH the ratio of (2) to (1) being at least 2.

10. The compound of claim 9 in which each R is the methyl radical.

11. A copolymeric compound free of Si-Si bonding consisting essentially of organosilicon units (1) of the formula -SiR in which m is a positive integer [from 2 to 3 inclusive, from one to two R substituents are OR' radicals in which R is a monovalent hydrocarbon radical free of aliphatic unsaturation, any remaining R radicals being rnonovalent hydrocarbon radicals free to aliphatic unsaturation, and units (2) of the formula 12. A copolymeric compound free of S'i-Si bonding consisting essentially of organosil-icon units (1) or" the formula 4iR (OR) in which each R is a monovalent hydrocarbon radical free of aliphatic unsaturation and units (2) of the formula CH CH:CHCH

13. The compound of claim 12 in which each R is the methyl radical.

14. A copolymeric compound free of Si-Si bonding consisting essentially of organosilicon units (1) of the formula SiR in which in is a positive integer from 2 to 3 inclusive, from one to two R substituents are -OR' radicals in which R is a mono-valent hydrocarbon radical free of aliphatic unsaturation, any remaining R radicals being monovalent hydrocarbon radicals free of aliphatic unsaturation, and units (2) of the formula 15. A copolymeri-c compound free of Si-Si bonding consisting essentially of organosilicon units 1) of the formula -SiR ,(OR) in which each R is a monovalent hydrocarbon radical tree of aliphatic unsaturation and units (2) of the formula References Cited by the Examiner UNITED STATES PATENTS OTHER REFERENCES Ryan et al.: Journal of Organic Chemistry, 24, 1959, 2052-53.

MURRAY TILLMAN, Primary Examiner.

MILTON STERMAN, I. R. LIBERMAN, WILLIAM H.

SHORT, Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,187,032 June 1, 1965 Donald R. Weyenberg It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 19, for "PhC=CH PhCH=CHpH" read Ph C=CH PhCH=CHPh column 3, in the table, second column, line 1 thereof, for "(C H )(CH SiCH( H )CH Si(CH (C H line 32, for "n read n column 7, line 74, for

1112 read D25.2

the top of the page, second column, line 5 thereof, for

(C H )(CH S1CH C(CH ]=CHCH S1(CH (C H same columns 7 and 8, in the table at the bottom of the page, second column, line 4 thereof, for "(CH SiOSi[OCH )(CI-I )OSi(CH 1 n I cn cmn read (CH3)3S1OS1(OCH3) (CH3)OS1(CH3)2CH2C(CH3] Columns 7 and 8, in the table at Signed and sealed this 10th day of May 1966.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. THE METHOD WHICH COMPRISES REACTING IN A SOLVENT SOLUTION IN CONTACT WITH AN ALKALI METAL AN ORGANOSILICON COMPOUND (1) SELECTED FROM THE GROUP CONSISTING OF HALOGENOSILANES OF THE FORMULA RMSIX4-M AND HALOGENOSILOXANES OF THE FORMULA RMX3-MSI(OSIR2)IX IN WHICH EACH R IS SELECTED FROM THE GROUP CONSISTING OF MONOVALENT HYDROCARBON RADICALS FREE OF ALIPHATIC UNSATURATION AND FUNCTIONAL SUBSTITUENTS SELECTED FROM THE GROUP CONSISTING OF THE HYDROGEN ATOM AND -OR'' RADICALS IN WHICH R'' IS A MONOVALENT HYDROCARBON RADICAL FREE OF ALIPHATIC UNSATURATION, EACH X IS A HALOGEN ATOM, EACH M IS A POSITIVE INTEGER FROM 2 TO 3 INCLUSIVE AND EACH N IS A POSITIVE INTEGER, AND A COMPOUND (2) SELECTED FROM THE GROUP CONSISTING OF (A) COMPOUNDS OF THE FORMULA R"2C=CHR" IN WHICH AT LEAST ONE R" SUBSTITUENT IS THE PHENYL RADICAL AND ANY REMAINING R" SUBSTITUENT IS SELECTED FROM THE GROUP CONSISTING OF THE HYDROGEN ATOM AND THE METHYL RADICAL, THERE BEING NO MORE THAN A TOTAL OF TWO PHENYL AND METHYL RADICALS, AND (B) COMPOUNDS OF THE FORMULA R''"CH=CH2 IN WHICH EACH R''" IS A SUBSTITUENT SELECTED FROM THE GROUP CONSISTING OF THE VINYL RADICAL AND THE ALPHA-METHYLVINYL RADICAL, WHEREBY THE SILICON ATOMS OF (1) ARE ATTACHED TO ALIPHATIC CARBON ATOMS OF (2) WITH THE ELIMINATION OF X ATOMS FROM (1).
 2. A COPOLYMERIC COMPOUND FREE OF SI-SI BONDING CONSISTING ESSENTIALLY OF ORGANOSILICON UNITS (1) SELECTED FROM THE GROUP CONSISTING OF UNITS OF THE FORMULAE -SIRM AND SIRM(OSIR2)N- IN WHICH AT LEAST ONE R PER UNIT IS A FUNCTIONAL SUBSTITUENT SELECTED FROM THE GROUP CONSISTING OF THE HYDROGEN ATOM AND -OR'' RADICALS IN WHICH R'' IS A MONOVALENT HYDROCARBON RADICAL FREE OF ALIPHATIC UNSATURATION, ANY REMAINING R RADICALS BEING MONOVALENT HYDROCARBON RADICALS FREE OF ALIPHATIC UNSATURATION, EACH M IS A POSITIVE INTEGER FROM 2 TO 3 INCLUSIVE AND EACH N IS A POSITIVE INTEGER, AND UNITS (2) OF THE FORMULA SELECTED FROM THE GROUP CONSISTING OF -CH2-CH=CH-CH2AND -CH2-C(CH3)=CH-CH2-. 